Process for the manufacture of intermediate products and new dyestuffs derived from diarylsulphones



7 phones, of which the following Patented Sept. ll, i923.

GUILLAUME DE MONTMOLLIN, OF BASEL,

SWITZERLAND, ASSIGNOE TO SOCIETY 013 iii F941! CAL INDUSTRY IN BASLE, OF BASEL, SWITZERLAND.

Pcnss roa ran a No Drawing.

To all whom it may concern:

Be itlmown that I, GUIILAUME on MONT- MOLLIN, a citizen of the Swiss Republic, residing at Basel, Switzerland, have invented new and useful Processes for the Manufacture of Intermediate Products and New Dyestuffs Derived from Diarylsu'lis a full, clear, and exact s ification.

In my earlier nited States Patent No. 1,359,969 I have described aminoazo lyestufis obtained by combining diazo derivatives of the mono-acidyl-diaminodiarylsulphones witlf fi-naphthylamine and its various substitution products.

By continuing -my researches on these lines I have synthesized a series of new sulfonated ortho-aminodiarylsulphones, characterized, on the one hand, by the presence of two benzene nuclei united by a SO group, and, on the other hand, by the presence of their d-iazotizable NH group in one of the ortho-positions in respect of the S0 group, and, finally, by that of a sO H group in one of the two benzene nuclei, which latter may of course carry other substituents yet, as for instance, halogens, CH NHCOR, etc., groups.

I have further found that there are obtained new acid dyestufis of great commercial value if the diam-derivatives of these sulphones, which contain the characteristic group are combined with non-sulfonated aromatic amines containing at least 10 atoms of carin which R, signifies the radicle of a sul- STUFFS DERIVED FROM DIARYLSULPHONES.

Application filed April 23, 1923. Serial No. 634,182.

fonated diphenylsulphone, and R the radicle of a non-sulfonated aromatic amine con-' taining at least 10 atoms of carbon all belonging of reducing agents they can be split into sulfonated' o-aminodiarylsulphones containingthe following characteristic group:

to aromatic nuclei. By the action vention without, however, limiting the same. Example 1.

41.3 parts of the diazo-deriva'tive of 2- amino 4 acetylamino 4-methyl-5'-sulfo-1-, l'-diphenylsulphone (obtained by condense tion of p-toluenesulfinic acid with 2.4-dinitro-l-chlorobenzene, sulfonation, reduction, acetylation and diazotation of the condensation product thus formed) are introduced into a solution of 20.7 parts hydrochloride of ethyl-B-naphthylamine. The dyestufi which is thus very rapidly formed is salted out in an alkaline solution and filtered. It constitutes, in a dry state, a brown-red powder dissolving in water to a bluish-red solution and in concentrated sulfuric acid to a brown solution. It dyes wool in a sulfuric acid bath in very to 1i ht and to washing Su stituting in this example the diazoderivative of 2-amino-4-acetylamino-4J- methyl-5-sulfo-1,1-diphenylsulphone by a equal bluish-red tints fast diam-derivative of 2-amino-5'-acetylam1no- 4 sulfo 1 methyl 1,1 diphenylsulphone (obtained by condensation of p-toluenesulfinic acid with l-chlom-Q-nitrobenzene-dsulfonic acid, nitration, reduction, acetylation and diazotation of the condensation product thus formed) there is obtained an analogous dyestufl", whilst the use of the diazo-derivative of the sulfonic acid of 2- amino 5 acetylamino -4'-methyl-1,1d1phenylsulphone (obtained by sulfonation and acetylation of the 2,5-diamino-4'-methyl-1, 1-diphenylsulphone of the German Patent No. 282,214) yields a visibly bluer product.

E mample 2.

stitutes a brick-red powder dissolving in water to a red solution and in concentrated sulfuric acid to a yellow-brown solution. It dyes wool in an acetic acid bath very uniform brick-red tints fast to light and to washing.

If the B-naphthylamine in this example is substituted by the phenyl-[l-naphthylamine there results a red dyestufi of analogous properties; the ethyl-aand-B-naphthylamines lead to bluish-red dyestufis.

E a'ample 3.

40.1 parts of the nitrated diazo-compound of 2 amino-l-sulfo-l'-Inethyl-1,1'-diphenylsulphone (obtained by condensation of ptoluenesulfinic acid with 1-chloro-2-nitrobenzene-t-sulfonic acid, reduction, diazotation and nitration of the condensation product thus formed) are introduced into a solution of 20.7 parts of ethyl-(l-naphthylamine. The dyestufi' is very rapidly formed. lit is salted out in an alkaline solution and filtered. In a dry form the dyestufi constitutes a red-brown powder dissolving in Water to a bluish-red, in concentrated sulturic acid to a brown solution. It dyes wool in an acetic acid bath very uniform bluishred tints fast to light and to washing.

E a'ample .4.

dyes wool in a sulfuric acid bath very equal orange tints, characterized by an excellent fastness to alkalis and to washing and a very good fastness to light.

With diphenylamine in place of the ethylbenzylaniline as coupling component, dyestufi's of a slightly browner appearance are obtained.

E aample 5.

To 35.6 parts of the diazo-derivative of 2-amino-4-sulfo-4'-methyl-1,1-diphenylsulphone, suspended in 500 parts of water, there is added an aqueous suspension of 18.3 parts of 'N-Inethyldiphenylamine. The coupling takes place very rapidly and is favored by a partial and careful neutralization of the free mineral acid. 7 The dyestuil is salted out in an alkaline solution and filtered. In a dry state it constitutes an orange-brown powder dissolving in water. to orange, in concentrated sulfuric acid to violet solutions. It dyes wool in an acetic acid bath very uniform full orange tints, characterized by an excellent fastness to alkalis and to washing and a very good fastness to light.

Substituting the N-methyldiphenylamine by methylbenzylaniline or ethylbenzylaniline there are obtainedorange dyestufis.

The diam-derivatives of 2-amino-4i-sulfo-1, 1'-diphenylsulphone or eventuall of 2- amino 4 sulfo 4C ch1oro-1,1'-diphenylsulphone (obtained according to the indications of example 2 from benzeneor p-chlorobenzenesulfinic acids) yield very similar dyestulls.

What I claim is:

1. The herein described new dyestufis obtained by uniting the diam-derivatives of the sulfonated ortho-amino-diarylsulphones with non-sulfonated aromotic amines con taining at least 10 atoms of carbon all helonging to aromatic nuclei and corresponding to the general formula:

and non-sulfonated aromatic diamines, constituting in a dry state powders varying from orange to brown, dissolving in Water woman from orange to bluish-red solutions, and in sulfuric acid from. yellow to brown and violet solutions, and dyeing wool in an acid bath bright tints varying from'orange to bluish-red of an excellent fastness to light in which R represents the radicle of a sulfonated diarylsulphone, and R that of a non-sulfonated aromatic amine other than a primary amine containing at least 10 atoms of carbon all belonging to aromatic nuclei,

which may be split under the action of reducing agents into sulfonated o-amino-dia-V rylsulphones containing the characteristic group lNHft,

, and non-sulfonated aromatic diamines, constituting in a dry state powders varying from orange to brown, dissolving in water from orange to bluish-red solutions, and in sulfuric acid from yellow to brown and violet solutions, and dyeing wool in an acid bath bright tints varying from orange to bluish-red of an excellent iastness to light and to washing.

3. The herein described new dyestufis obtained by uniting the diazo-derivatives of the sulfonated ortho-amino-diarylsulphones with non-sulfonated aromatic amines other than primary amines containing atleast 12 atoms of carbon all belonging to aromatic nuclei and corresponding to the general formula:

i lit N:NR

in which R represents the radicle of a sulfonated diarylsulphone, and R that of a non-sulfonated aromatic amine other than a primary amine containing at least 12 atoms of carbon all belonging to aromatic nuclei, which may be split under the action of reducing agents into sulfonated o-amino-(liarylsulphones containing the characteristic group \w; C/A k/ and non-sulfonated aromatic diamines, constituting in a dry state powders varying from orange to brown, dissolving in water from orange to bluish-red solutions, and in sulfuric acid from yellow to brown and violet, solutions, and dyeing wool in an acid bath bright tints varying from orange to bluish-red of an excellent fastness to light and to washing.

In witness whereof have hereunto signed my name this 10th day of April 1923, in the presence of two subscribing witnesses.

GUMAUME da- MONH'MOUJN.

Witnesses:

ARMANI BAUME, L cmN J. Promo. 

